Nanocomposite Films of Silver Nanoparticles and Conjugated Copolymer in Natural and Nano-Form: Structural and Morphological Studies.

The use of conjugated polymers (CPs) and metallic nanoparticles is an interesting way to form nanocomposites with improved optical properties. For instance, a nanocomposite with high sensitivity can be produced. However, the hydrophobicity of CPs may hamper applications due to their low bioavailability and low operability in aqueous media. This problem can be overcome by forming thin solid films from an aqueous dispersion containing small CP nanoparticles. So, in this work we developed the formation of thin films of poly(9,9-dioctylfluorene-co-3,4-ethylenedioxythiophene) (PDOF-co-PEDOT) from its natural and nano form (NCP) from aqueous solution. These copolymers were then blended in films with triangular and spherical silver nanoparticles (AgNP) for future applicability as a SERS sensor of pesticides. TEM characterization showed that the AgNP were adsorbed on the NCP surface, forming a nanostructure with an average diameter of 90 nm (value according to that obtained by DLS) and with a negative potential zeta. These nanostructures were transferred to a solid substrate, forming thin and homogeneous films with different morphology of PDOF-co-PEDOT films, as observed by atomic force microscopy (AFM). XPS data demonstrated the presence of the AgNP in the thin films, as well as evidence that films with NCP are more resistant to the photo-oxidation process. Raman spectra showed characteristic peaks of the copolymer in the films prepared with NCP. It should also be noted the enhancement effect of Raman bands observed on films containing AgNP, a strong indication of the SERS effect induced by the metallic nanoparticles. Furthermore, the different geometry of the AgNP influences the way in which the adsorption between the NCP and the metal surface occurs, with a perpendicular adsorption between the NCP chains and the surface of the triangular AgNP.

The Influence of Alkali Metals on the Doping of Poly(p-phenylene) Oligomers.

In this study, we report on crystallographic studies that were performed on Na- and K-doped terphenyl and quaterphenyl. The data obtained via X-ray scattering and transmission electron diffraction show that, for both K-doped terphenyl and quaterphenyl samples, there is an increase in the c parameter. However, in regard to Na-doped terphenyl, there is a c parameter decrease along with an a parameter increase, which may be accounted for by the polymerization of this oligomer. Moreover, in order to complete the crystallographic study, a Raman analysis was conducted to describe the localization of the radical anions and the local distortions induced by the electric charges during the doping process.

Efficient and Facile Synthetic Route of MoO3:MoS2 Hybrid Thin Layer via Oxidative Reaction of MoS2 Nanoflakes.

In the present study, MoO3:MoS2 hybrid thin layers have been synthesized through partial oxidation of MoS2. We have demonstrated that the reaction requires darkness conditions to decrease the oxidation rate, thus obtaining the hybrid, MoO3:MoS2. A simple liquid-phase exfoliation (LPE) is carried out to achieve homogenous MoS2 nanoflakes and high reproducibility of the results after MoS2 oxidation. XPS analyses reveal the presence of MoO3, MoS2, and MoOxSy in the hybrid layer. These results are also confirmed by X-ray diffraction and high-resolution TEM. Optical absorbance reveals that the absorption peaks of the MoO3:MoS2 hybrid are slightly redshifted with the appearance of absorption peaks in the near-infrared region due to the defects created after the oxidation reaction. The composition and atomic percentages of each component in the hybrid layer as a function of reaction time have also been reported to give perspective guides for improving electronic and optoelectronic devices based on 2D-MoS2.

Power Conversion Efficiency Improvement of Planar Organic Photovoltaic Cells Using an Original Hybrid Electron-Transporting Layer.

In organic photovoltaic (OPV) cells, besides the organic active layer, the electron-transporting layer (ETL) has a primordial role in transporting electrons and blocking holes. In planar heterojunction-OPVs (PHJ-OPVs), the ETL is called the exciton blocking layer (EBL). The optimum thickness of the EBL is 9 nm. However, in the case of inverted OPVs, such thickness is too high to permit efficient electron collection, due to the fact that there is no possibility of metal diffusion in the EBL during the top metal electrode deposition. In the present work, we show that the introduction of a thin potassium layer between the indium tin oxide (ITO) cathode and the EBL increases dramatically the conductivity of the EBL. We demonstrate that K not only behaves as a simple ultrathin layer allowing for the discrimination of the charge carriers at the cathode/organic material interface but also by diffusing into the EBL, it increases its conductivity by 3 orders of magnitude, which allows us to improve the shape of the J-V characteristics and the PHJ-inverted OPV efficiency by more than 33%. Moreover, we also show that PHJ-inverted OPVs with K in their EBLs are more stable than those with Alq3 alone.

Semi-Transparent Organic Photovoltaic Cells with Dielectric/Metal/Dielectric Top Electrode: Influence of the Metal on Their Performances.

In order to grow semi-transparent organic photovoltaic cells (OPVs), multilayer dielectric/metal/dielectric (D/M/D) structures are used as a transparent top electrode in inverted OPVs. Two different electrodes are probed, MoO3/Ag/MoO3 and MoO3/Ag/Cu:Ag/ZnS. Both of them exhibit high transmission in visible and small sheet resistance. Semi-transparent inverted OPVs using these electrodes as the top anode are probed. The active organic layers consist in the SubPc/C60 couple. The dependence of the OPV performances on the top electrode was investigated. The results show that far better results are achieved when the top anode MoO3/Ag/MoO3 is used. The OPV efficiency obtained was only 20% smaller in comparison with the opaque OPV, but with a transparency of nearly 50% in a broad range of the visible light (400-600 nm). In the case of MoO3/Ag/Cu:Ag/ZnS top anode, the small efficiency obtained is due to the presence of some Cu diffusion in the MoO3 layer, which degrades the contact anode/organic material.

Linear chains of Ag nanoparticles embedded in dielectric films for SERS applications in analytical chemistry.

In line with the approach known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), in which Raman signal amplification of analytes is provided by metallic nanoparticles with an ultrathin silica or alumina shell, we report here on a Surface-Enhanced Raman Spectroscopy (SERS) substrate consisting of periodic lines of Ag nanoparticles embedded in dielectric surfaces for enhancing Raman signals. This paper demonstrates the possibility to use these so-called 'PLANEDSERS' substrates as washable and reusable chemical sensors with a good level of repeatability. Large-area Ag nanoparticle arrays are produced by glancing-angle ion-beam sputtering deposition on nanorippled patterns and are protected from the chemical environment (atmospheric or liquid solutions) by a robust and functionalizable thin dielectric layer of alumina or silicon nitride. Our results show that linear assemblies of ellipsoidal nanoparticles (size ∼15 nm) separated by interparticle gaps of approximately 5 nm generate enough near-field intensity enhancement to give rise to significant SERS signals of non-Raman-resonant bipyridine molecules without chemical contact between molecules and Ag nanoparticles. Moreover, the optical dichroic response of these plasmonic assemblies allows for the possibility of tuning the excitation wavelength of the Raman spectra over a wide spectral range. This study is a first step towards designing a substrate-platform without chemical specificity to enhance in equal manner all the weak Raman signals of usual organic molecules and to avoid loss of balance in favour of only one species as usual in SERS experiments. The quantitative detection ranges for bipyridine used as a probe test molecule are around between 10-3 to 10-6 M.

Chemical functionalization of nano fibrillated cellulose by glycidyl silane coupling agents: A grafted silane network characterization study.

Nano fibrillated cellulose (NFC) has turned into a material widely studied due to its desirable performance for numerous organic systems. Nevertheless, its surface is not very compatible with most organic systems; hence, chemical functionalization methods offer a path to solve this problem. In this study, NFC is successfully functionalized with two silane coupling agents: 3-glycidyloxypropyl trimethoxysilane (GPS) and 3-glycidyloxypropyl dimethylethoxysilane (GPMES) by a simple, direct, and environmentally friendly method. Different analyses have been carried out in order to confirm the chemical modification of NFC. ATR-IR, XPS, and 29Si NMR spectroscopies confirmed the chemical modification that allowed the understanding of the structure and the conformation onto the modified NFC surface. SEM and AFM microscopies were performed to study possible alterations in morphology; a slight change was observed. Thermal properties were also analyzed by TGA analysis. It remains stable after chemical functionalization. Grafted NFC showed good performance compared to the pristine one. It allows a better dispersion into organic systems improving their properties.

Biocompatibility and osseointegration of nanostructured titanium dental implants in minipigs.

OBJECTIVES: It is well known that surface treatments of dental implants have a great impact on their rate of osseointegration. The aim of this study was to compare the biocompatibility and the bone-implant contact (BIC) of titanium dental implants with different surface treatments. MATERIAL AND METHODS: Test implants (Biotech Dental) had a nanostructured surface and control implants (Anthogyr) were grit-blasted with biphasic calcium phosphate and acid-etched surface. Both titanium implants were inserted in mandible and maxillary bones of 6 Yucatan minipigs for 4 and 12 weeks (n = 10 implants/group). Biocompatibility and osseointegration were evaluated by non-decalcified histology and back-scattered electron microscopy images. RESULTS: The reading of histology sections by an antomo-pathologist indicated that the test implants were considered non-irritating to the surrounding tissues and thus biocompatible compared with control implants. The BIC values were higher for test than for control dental implants at both 4 and 12 weeks. CONCLUSIONS: In summary, the new nanostructured titanium dental implant is considered biocompatible and showed a better osseointegration than the control implant at both 4 and 12 weeks.

Rotator Cuff Tenocytes Differentiate into Hypertrophic Chondrocyte-Like Cells to Produce Calcium Deposits in an Alkaline Phosphatase-Dependent Manner.

Calcific tendonitis is a frequent cause of chronic shoulder pain. Its cause is currently poorly known. The objectives of this study were to better characterize the cells and mechanisms involved in depositing apatite crystals in human tendons. Histologic sections of cadaveric calcified tendons were analyzed, and human calcific deposits from patients undergoing lavage of their calcification were obtained to perform infrared spectroscopy and mass spectrometry-based proteomic characterizations. In vitro, the mineralization ability of human rotator cuff cells from osteoarthritis donors was assessed by alizarin red or Von Kossa staining. Calcifications were amorphous areas surrounded by a fibrocartilaginous metaplasia containing hypertrophic chondrocyte-like cells that expressed tissue non-specific alkaline phosphatase (TNAP) and ectonucleotide pyrophosphatase/phosphodiesterase 1 (ENPP1), which are two key enzymes of the mineralization process. Calcific deposits were composed of apatite crystals associated with proteins involved in bone and cartilage development and endochondral bone growth. In vitro, tenocyte-like cells extracted from the rotator cuff were able to mineralize in osteogenic cultures, and expressed TNAP, type X COLLAGEN, and MMP13, which are hypertrophic chondrocytes markers. The use of a TNAP inhibitor significantly prevented mineral deposits. We provide evidence that tenocytes have a propensity to differentiate into hypertrophic chondrocyte-like cells to produce TNAP-dependent calcium deposits. We believe that these results may pave the way to identifying regulating factors that might represent valuable targets in calcific tendonitis.

Facile enhancement of bulk heterojunction solar cells performance by utilizing PbSe nanorods decorated with graphene.

An efficient approach for improving the photoelectrical conversion efficiency (PCE) of the bulk heterojunction (BHJ) solar cells, based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61 butyric acidmethyl ester (PC61BM), by incorporating PbSe nanorods decorated with graphene (G) into their active layer has been reported for the first time. Pristine PbSe and PbSe:G composites (with different amount of graphene) are synthesized via hydrothermal process and the formation mechanism is explained. The systematic investigation indicates that the crystallite size of PbSe:G increases with increasing graphene content. The PCE of the classical BHJ solar cells based on P3HT:PC61BM is improved from 2.32 up to 2.57% by the incorporation of pristine PbSe. It is also enhanced by the incorporation of PbSe:G up to certain composition of graphene in which a maximum PCE value of 5.16% is achieved. The external quantum efficiency of the BHJ solar cells is also investigated. The photovoltaic parameters are discussed based on the morphology variation detected by scanning electron microscope and atomic force microscope of the active layers together with their UV-VIS absorption measurements.

AFM-Nano Manipulation of Plasmonic Molecules Used as "Nano-Lens" to Enhance Raman of Individual Nano-Objects.

This paper explores the enhancement of Raman signals using individual nano-plasmonic structures and demonstrates the possibility to obtain controlled gold plasmonic nanostructures by atomic force microscopy (AFM) manipulation under a confocal Raman device. By manipulating the gold nanoparticles (Nps) while monitoring them using a confocal microscope, it is possible to generate individual nano- structures, plasmonic molecules not accessible currently by lithography at these nanometer scales. This flexible approach allows us to tune plasmonic resonance of the nanostructures, to generate localized hot spots and to circumvent the effects of strong electric near field gradients intrinsic to Tip Enhanced Raman Spectroscopy (TERS) or Surface Enhanced Raman Spectroscopy (SERS) experiments. The inter Np distances and symmetry of the plasmonic molecules in interaction with other individual nano-objects control the resonance conditions of the assemblies and the enhancement of their Raman responses. This paper shows also how some plasmonic structures generate localized nanometric areas with high electric field magnitude without strong gradient. These last plasmonic molecules may be used as "nano-lenses" tunable in wavelength and able to enhance Raman signals of neighbored nano-object. The positioning of one individual probed nano-object in the spatial area defined by the nano-lens becomes then very non-restrictive, contrary to TERS experiments where the spacing distance between tip and sample is crucial. The experimental flexibility obtained in these approaches is illustrated here by the enhanced Raman scatterings of carbon nanotube.

Colorectal Cancer Cells Adhere to and Migrate Along the Neurons of the Enteric Nervous System.

BACKGROUND & AIMS: In several types of cancers, tumor cells invade adjacent tissues by migrating along the resident nerves of the tumor microenvironment. This process, called perineural invasion, typically occurs along extrinsic nerves, with Schwann cells providing physical guidance for the tumor cells. However, in the colorectal cancer microenvironment, the most abundant nervous structures belong to the nonmyelinated intrinsic enteric nervous system (ENS). In this study, we investigated whether colon cancer cells interact with the ENS. METHODS: Tumor epithelial cells (TECs) from human primary colon adenocarcinomas and cell lines were cocultured with primary cultures of ENS and cultures of human ENS plexus explants. By combining confocal and atomic force microscopy, as well as video microscopy, we assessed tumor cell adhesion and migration on the ENS. We identified the adhesion proteins involved using a proteomics approach based on biotin/streptavidin interaction, and their implication was confirmed further using selective blocking antibodies. RESULTS: TEC adhered preferentially and with stronger adhesion forces to enteric nervous structures than to mesenchymal cells. TEC adhesion to ENS involved direct interactions with enteric neurons. Enteric neuron removal from ENS cultures led to a significant decrease in tumor cell adhesion. TECs migrated significantly longer and further when adherent on ENS compared with on mesenchymal cells, and their trajectory faithfully followed ENS structures. Blocking N-cadherin and L1CAM decreased TEC migration along ENS structures. CONCLUSIONS: Our data show that the enteric neuronal network guides tumor cell migration, partly via L1CAM and N-cadherin. These results open a new avenue of research on the underlying mechanisms and consequences of perineural invasion in colorectal cancer.

A new way to discriminate polluted wood by vibrational spectroscopies.

In this work, two sets of samples were considered: field samples collected from local waste wood and synthetic samples made by mixing clean wood (including oak, beech, poplar) with typical organic pollutants: creosote, polychlorinated byphenils (PCBs), pentachlorophenol (PCP), cypermethrin, dodecyl dimethyl ammonium chloride (DDAC). Vibrational spectroscopy techniques were tested to detect organic pollutants in wood items. Raman and infrared spectroscopies were showed as fast, non-destructive and non-invasive fingerprint techniques for detection of organic molecules. Associated with principal component analysis, we have shown the evidence of quick detection of and discrimination of polluted wood items by kinds and versus concentration.

Comparative bone tissue integration of nanostructured and microroughened dental implants.

AIM: The aim was to compare osteointegration of nanostructured implants to a microsurface widely used for titanium dental implants. MATERIALS & METHODS: Commercial titanium dental implants with smooth or microroughened surfaces were nanostructured. Implants were inserted into the femoral condyles of rabbits. After 2 and 4 weeks, histomorphometry calculation was performed. RESULTS: Nanotubes measuring 60 nm in diameter were observed on both S-NANO (roughness: 0.05 µm) and R-NANO (roughness: 0.40 µm) surfaces. The MICRO surface exhibited typical random cavities (roughness: 2.09 µm). At 4 weeks, bone-to-implant contact values were significantly higher for the R-NANO than for the MICRO surface while no differences were observed at 2 weeks. CONCLUSION: Overall, this study shows that the nanostructured surfaces improved osteointegration similar or higher than the MICRO.

Raman changes induced by electrochemical oxidation of poly(triarylamine)s: toward a relationship between molecular structure modifications and charge generation.

Linear, alternating polymers of aromatic amines (p-phenylenediamine, bis(p-aminophenyl)amine, and diaminocarbazole) and either m-phenylene or 3,5-pyridine have been synthesized and characterized by electrochemical and spectroscopic means. The presence of radical cations in their electrochemically oxidized forms is manifested by new bands in the UV-vis-NIR spectra whose appearance can be correlated with reversible redox couples registered in the corresponding cyclic voltammograms at approximately the same potentials as well as with pronounced evolutions of their resonance Raman spectra. Detailed analysis of the Raman data gives information about the locations and the distribution of radical cations and spinless dication in the macromolecule. This approach can provide a new insight into the formation of high-spin states in these polymers.

Enhanced osseointegration of titanium implants with nanostructured surfaces: an experimental study in rabbits.

Titanium and its alloys are commonly used for dental implants because of their good mechanical properties and biocompatibility. The surface properties of titanium implants are key factors for rapid and stable bone tissue integration. Micro-rough surfaces are commonly prepared by grit-blasting and acid-etching. However, proteins and cells interact with implant surfaces in the nanometer range. The aim of this study was to compare the osseointegration of machined (MA), standard alumina grit-blasted and acid-etched (MICRO) and nanostructured (NANO) implants in rabbit femurs. The MICRO surface exhibited typical random cavities with an average roughness of 1.5 µm, while the NANO surface consisted of a regular array of titanium oxide nanotubes 37±11 nm in diameter and 160 nm thick. The MA and NANO surfaces had a similar average roughness of 0.5 µm. The three groups of implants were inserted into the femoral condyles of New Zealand White rabbits. After 4 weeks, the pull-out test gave higher values for the NANO than for the other groups. Histology corroborated a direct apposition of bone tissue on to the NANO surface. Both the bone-to-implant contact and bone growth values were higher for the NANO than for the other implant surfaces. Overall, this study shows that the nanostructured surface improved the osseointegration of titanium implants and may be an alternative to conventional grit-blasted and acid-etched surface treatments.

Osteoblastic and osteoclastic differentiation of human mesenchymal stem cells and monocytes in a miniaturized three-dimensional culture with mineral granules.

The pathologies of the skeleton have a significant socioeconomic impact on our population. Although therapies have improved the treatment of osteosarcoma and osteoporosis, their efficacy still remains limited. In this context, we developed a miniaturized 3-D culture model of bone cells on calcium phosphate ceramics. Human bone marrow mesenchymal stem cells (MSCs) were three-dimensionally cultured on particles of biphasic calcium phosphate (BCP, 125-200µm) in osteogenic media. The MSCs seeded on the BCP particles adhered and proliferated, producing abundant collagenous extracellular matrix (ECM). Light and confocal laser scanning microscopy showed that the MSCs created bridges between the BCP particles and formed a 3-D structure. Energy dispersive X-ray analysis in a scanning electron microscope confirmed the mineralization of the collagen matrix. The 96-well sized bone constructs were tested by immunohistology and transcription analysis, proving cell differentiation. Both techniques corroborated the osteoblastic differentiation with high production of bone sialoprotein and osteocalcin. Peripheral blood CD14-positive monocytes (MOs) were pre-differentiated into osteoclasts prior to seeding on the 3-D constructs. Multinucleated and tartrate-resistant acid phosphatase-positive cells were also identified at the surface of the 3-D constructs after 90days of culture. In addition, cell viability within these constructs was measured by flow cytometry. In summary, we have developed a miniaturized 3-D culture of bone cell precursors with osteoblasts and osteoclasts. This 3-D culture may make it possible to test the effects of new drugs for bone healing, osteoporosis and osteosarcomas, in more appropriate cell-cell and cell-matrix interactions than conventional 2-D cultures.

Assessment of DNA binding to human Rad51 protein by using quartz crystal microbalance and atomic force microscopy: effects of ADP and BRC4-28 peptide inhibitor.

The interaction of human Rad51 protein (HsRad51) with single-stranded deoxyribonucleic acid (ssDNA) was investigated by using quartz crystal microbalance (QCM) monitoring and atomic force microscopy (AFM) visualization. Gold surfaces for QCM and AFM were modified by electrografting of the in situ generated aryldiazonium salt from the sulfanilic acid to obtain the organic layer Au-ArSO3 H. The Au-ArSO3 H layer was activated by using a solution of PCl5 in CH2 Cl2 to give a Au-ArSO2 Cl layer. The modified surface was then used to immobilize long ssDNA molecules. The results obtained showed that the presence of adenosine diphosphate promotes the protein autoassociation rather than nucleation around DNA. In addition, when the BRC4-28 peptide inhibitor was used, both QCM and AFM confirmed the inhibitory effect of BRC4-28 toward HsRad51 autoassociation. Altogether these results show the suitability of this modified surface to investigate the kinetics and structure of DNA-protein interactions and for the screening of inhibitors.

Vibrational dynamics in dendridic oligoarylamines by Raman spectroscopy and incoherent inelastic neutron scattering.

Vibrational dynamics in triarylamine dendrimers was studied in a complementary way by Raman and infrared (IR) spectroscopies and incoherent inelastic neutron scattering (IINS). Three molecules were investigated, namely, unsubstituted triarylamine dendrimer of the first generation and two dendrimers of the first and second generation, substituted in the crown with butyl groups. To facilitate the assignment of the observed IR and Raman modes as well as the IINS peaks, vibrational models, based on the general valence force field method (GVFF), were calculated for all three compounds studied. A perfect consistency between the calculated and experimental results was found. Moreover, an important complementarity of the vibrational spectroscopies and IINS was established for the investigated dendrimers. The IINS peaks originating mainly from the C-H motions were not restricted by particular selection rules and only dependent on the IINS cross section. To the contrary, Raman and IR bands were imposed by the selection rules and the local geometry of the dendrimers yielding mainly C-C and C-N deformation modes with those of C-H nature of much lower intensity. Raman spectroscopy was also applied to the studies of the oxidation of dendrimers to their cationic forms. A strong Raman resonance effect was observed, since the spectra of the studied compounds, registered at different levels of their oxidation, strongly depended on the position of the excitation line with respect to their electronic spectrum. In particular, the blue (458 nm) excitation line turned out to be insensitive toward the cationic forms yielding very limited spectral information. To the contrary, the use of the red (647 nm) and infrared (1064 nm) excitation lines allowed for an unambiguous monitoring of the spectral changes in dendrimers oxidized to nominally monocationic and tricationic states. The analysis of oxidation-induced spectral changes in the tricationic state indicated that the charge storage configuration predominantly involved one spinless dication of the quinoid bond sequence and one radical cation. However, small numbers of dications were also found in a nominally monocationic state, where only radical cations should have been present. This finding was indicative of some inhomogeneity of the oxidation.

Strong improvements of localized surface plasmon resonance sensitivity by using Au/Ag bimetallic nanostructures modified with polydopamine films.

In the present work, the standard monometallic localized surface plasmon resonance (LSPR) biosensing sensitivity is highly improved when using a new system based on glass substrates modified with high-temperature annealed gold/silver bimetallic nanoparticles (Au/Ag bimetallic NPs) coated with polydopamine films before biomolecule specific immobilization. Thus, different zones of bimetallic NPs are spatially created onto a glass support thanks to a commercial transmission electron microscopy (TEM) grid marker in combination with two sequential evaporations of continuous films of gold (4 nm) and silver (2 nm) and followed by annealing at 500 °C for 8 h. By using the scanning electron microscopy (SEM), it is found that annealed Au/Ag bimetallic NPs have uniform size and shape distribution that exhibited a sharper well-defined LSPR resonant peak when compared with that of monometallic Au NPs and thereby contributing to an improved sensitivity in LSPR biosensor application. The controlled micropatterns consisting of bimetallic particles are used in the construction of LSPR biochips for high-throughput detection of different concentrations of a model antigen named bovine serum albumin (BSA) on a single glass sample, with a lower limit of detection of 0.01 ng/mL under the optimized conditions.